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United States Patent |
5,702,642
|
Yamada
,   et al.
|
December 30, 1997
|
Polymeric compounds, and liquid crystal element using the same
Abstract
The polymeric compound of this invention is represented by the following
general formula (I):
##STR1##
wherein A represents a hydrogen atom or
##STR2##
B represents a hydrogen atom or
##STR3##
each of X.sub.1 and X.sub.2 represents independently a hydrogen atom or a
methyl group, each of m and n represents independently an integer of 0 to
14, each of p and q represents independently 0 or 1, and each of Y1 ,
Y.sub.2, Y.sub.3, and Y.sub.4 represents independently a hydrogen atom or
a fluorine atom, with the proviso that both A and B are not hydrogen
atoms, p is 0 when m is 0, and q is 0 when n is 0. The liquid crystal
display element of this invention includes a pair of substrates oppositely
disposed with a gap therebetween, and a liquid crystal layer placed in
said gap, at least one of said substrates being transparent, and said
liquid crystal layer having a liquid crystal region, and a polymer wall
surrounded by said liquid crystal region, wherein said liquid crystal
layer includes a liquid crystal material, a polymeric polymer material,
and the above-described polymeric compound. The liquid crystal display
element prepared from the polymeric compound of this invention does not
cause disclination lines, and has bright characteristics in the absence of
an electric voltage.
Inventors:
|
Yamada; Nobuaki (Higashiosaka, JP);
Kozaki; Shuichi (Nara, JP);
Mizobe; Hoyo (Soka, JP);
Yoshida; Masahiko (Soka, JP);
Suzuki; Kenji (Soka, JP)
|
Assignee:
|
Sharp Kabushiki Kaisha (Osaka, JP);
Kanto Kagaku Kabushiki Kaisha (Tokyo, JP)
|
Appl. No.:
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797348 |
Filed:
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February 11, 1997 |
Foreign Application Priority Data
Current U.S. Class: |
252/299.66; 349/183; 526/245; 526/251; 526/304 |
Intern'l Class: |
C09K 019/12; G02F 001/133.3; C08F 020/30 |
Field of Search: |
252/299.66
349/183
526/251,245,304
|
References Cited
U.S. Patent Documents
4596445 | Jun., 1986 | Fergason | 350/339.
|
4662720 | May., 1987 | Fergason | 350/339.
|
5426009 | Jun., 1995 | Coates et al. | 430/20.
|
5518652 | May., 1996 | Parri et al. | 252/299.
|
Foreign Patent Documents |
32 23 104 A1 | Jun., 1982 | DE.
| |
42 26 994 A1 | Aug., 1992 | DE.
| |
62-70406 | Mar., 1962 | JP.
| |
58-501631 | Sep., 1983 | JP.
| |
5-226322 | Dec., 1984 | JP.
| |
61-502128 | Sep., 1986 | JP.
| |
1-269922 | Oct., 1989 | JP.
| |
2-99920 | Apr., 1990 | JP.
| |
2-153319 | Jun., 1990 | JP.
| |
2-153318 | Jun., 1990 | JP.
| |
3-61925 | Mar., 1991 | JP.
| |
3-278024 | Dec., 1991 | JP.
| |
4-31824 | Feb., 1992 | JP.
| |
4-212928 | Aug., 1992 | JP.
| |
4-338923 | Nov., 1992 | JP.
| |
5-11237 | Jan., 1993 | JP.
| |
5-27242 | Feb., 1993 | JP.
| |
5-281519 | Oct., 1993 | JP.
| |
5-257135 | Oct., 1993 | JP.
| |
2 267 105 | Jun., 1992 | GB.
| |
WO 83/01016 | Mar., 1983 | WO.
| |
WO 85/04262 | Sep., 1985 | WO.
| |
9322397 | Nov., 1993 | WO.
| |
Other References
Handbook of Liquid Crystals, Kelker, Hatz, Weinheim, pp. 35, 37 (1980).
Flussige Kristalle in Tab., Dt. Verlag f. Grundstoffindustrie, Leipzig
1974.
CA 115:9618--1990.
CA 113:41443--1990.
CA 112:199209--1988.
CA 120:285256--1993.
CA 87:215928--1978.
|
Primary Examiner: Wu; Shean C.
Attorney, Agent or Firm: Conlin; David G., Neuner; George W.
Parent Case Text
This is a continuation of copending application Ser. No. 08/466,042 filed
on Jun. 6, 1995.
Claims
What is claimed is:
1. A polymeric compound represented by the following general formula (I):
##STR48##
wherein A represents
##STR49##
B represents
##STR50##
each of X.sub.1 and X.sub.2 represents independently a hydrogen atom or a
methyl group, each of m and n represents independently an integer of 0 to
14, and each of Y.sub.3 and Y.sub.4 represents independently a hydrogen
atom or a fluorine atom.
2. The polymeric compound of claim 1, wherein in the general formula (I)
each of m and n represents independently an integer of 2 to 12.
3. A liquid crystal display element comprising a pair of substrates
oppositely disposed with a gap therebetween, and a liquid crystal layer in
said gap, at least one of said substrates being transparent,
said liquid crystal layer having a liquid crystal region and a polymer wall
surrounding said liquid crystal region,
wherein said liquid crystal layer includes a liquid crystal material, a
polymeric polymer material, and the polymeric compound of claim 1.
4. The liquid crystal display element of claim 3, wherein said liquid
crystal region comprises liquid crystal molecules, and the orientation of
said liquid crystal molecules is either random, radial, concentric or
spiral.
5. The liquid crystal display element of claim 3, wherein an alignment film
is placed on said substrates.
6. The liquid crystal display element of claim 3, wherein said liquid
crystal region comprises liquid crystal molecules, and the orientation of
said liquid crystal molecules is TN, STN, ECB or FLC.
7. The liquid crystal display element of claim 3, wherein said polymeric
polymer material is a photocurable resin.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to polymeric compounds which increase, in a
liquid crystal display element comprising a liquid crystal layer having a
polymer wall and a liquid crystal region substantially surrounded by said
polymer wall, the orientation restricting force of a liquid crystal
material present in said liquid crystal regions in an interface between
said liquid crystal material and said polymer wall, and also relates to a
liquid crystal display element using the polymeric compound. The liquid
crystal display element of this invention can be utilized for personal
display devices such as word processors, personal computers, and the like.
The liquid crystal display element can also be utilized in devices used by
a number of people such as portable information end devices, and the like.
2. Description of the Related Art
Liquid crystal display elements using a liquid crystal material and a
polymer material:
(1) Japanese Laid-open Patent Publication No. 58-501631 discloses, a
polymer dispersed liquid crystal display element which comprises a polymer
material and a liquid crystal material encapsulated by the polymer
material which displays the scattering state of an incident light by the
refractive index difference between the liquid crystal material and the
polymer material, and also displays the transparent state by the variation
of the refractive index of the liquid crystal material with the impression
of an electric voltage.
Japanese Laid-open Patent Publication No. 61-502128 discloses a liquid
crystal display element comprising a liquid crystal layer in which the
phases of the liquid crystal material and the cured resin are
three-dimensionally separated by irradiating a mixture of the liquid
crystal material and the photocurable resin with ultraviolet ray.
These elements are basically liquid crystal display elements which control
electrically the scattering-transparency variation of an incident light in
the liquid crystal layer.
(2) Japanese Laid-open Patent Publication No. 1-269922 discloses a
technique for preparing liquid crystal regions with different
characteristics by first exposing to ultraviolet ray a liquid crystal
layer comprising a photocurable resin and a liquid crystal material
through a photo-mask, and further irradiating it with ultraviolet ray
after remove the photo-mask. The element thus obtained is basically a
scattering type element.
Japanese Laid-open Patent Publication No. 5-257135 discloses an element
comprising a liquid crystal layer obtained by oppositely placing a
substrate equipped with an alignment film having an orientation
restricting force through a pair of gaps, injecting a mixture of a liquid
crystal material and a photocurable resin into the gaps, and then
irradiating the mixture with ultraviolet rays through a photo-mask
disposed on the surface of said substrate. Since the inner portion of the
liquid crystal layer in which the photo-mask is disposed has different
threshold values and different optical characteristics obtained from the
impression of an electric voltage from those of the outer portion of the
liquid crystal layer, the element is a static driving element in which the
pixel patterns are varied due to the electric voltage.
The principal behind the improvement of the viewing angle characteristics
of a liquid crystal display element:
In order to improve the viewing angle characteristics of a liquid crystal
display element, it is necessary to orient each of the liquid crystal
molecule toward three or more different directions inside the pixels
(liquid crystal regions). If each of the liquid crystal molecules inside
the liquid crystal layer is oriented in three or more different
directions, the apparent refractive index of each of the liquid crystal
molecules is averaged in the gray scale state when viewing the pixels from
both A and B directions as described in FIG. l(b). In other words, the
contrast of the display element is substantially identical from both A and
B directions. Therefore, the viewing angle characteristics of the element
having such an orientation state of the liquid crystal as shown in FIG.
1(b) are improved, compared to those of the element having a TN mode shown
in FIG. 2.
Specific examples of the elements having a wide viewing angle mode:
(1) Japanese Laid-open Patent Publications Nos. 4-338923 and 4-212928
disclose a wide viewing angle mode comprising a combination of the
aforementioned polymer dispersed liquid crystal element and polarizing
plates, which are attached to both surfaces of the element such that each
of the polarization axes of the plates are at a right angle to each other.
(2) As a method for improving the viewing angle characteristics of a
non-scattering type liquid crystal display element using a polarizer,
Japanese Laid-open Patent Publication No. 5-27242 discloses a method for
preparing a composite material of a liquid crystal and a polymer from a
mixture of the liquid crystal and a photocurable resin by the phase
separation. According to this method, the orientation of the liquid
crystal domains becomes random due to the polymer thus prepared.
Therefore, because the liquid crystal molecules are oriented in different
directions in each domain at the time of impressing an electric voltage,
the apparent refractive indices viewed from each direction are
substantially identical, and the viewing angle characteristics are
improved in the gray scale state.
(3) In recent years, the present inventors have proposed a liquid crystal
display element comprising a liquid crystal region in which the liquid
crystal molecules are omnidirectionally (spirally) oriented in the
portions where a photo-mask is present, and a polymer wall which consists
mainly of a photocurable resin in the other portions. The liquid crystal
region and polymer wall are formed by irradiating through the photo-mask a
cell having a liquid crystal composition comprising the photocurable resin
and the liquid crystal material. When the liquid crystal molecules of the
liquid crystal display element are controlled by an electric voltage, the
spiral orientation of the liquid crystal molecules will act as if an
umbrella opened and closed to improve significantly the viewing angle
characteristics.
In the interface between the polymer wall and the liquid crystal material
of the element described in (3), disclination lines are generated due to
the reverse tilt of the liquid crystal molecules at the time of impressing
an electric voltage. Since the disclination lines are displayed as bright
lines, the viewing angle characteristics of the element are deteriorated,
when the display state is in a black state.
The prevent inventors have found that the addition of a polymeric compound
to a mixture of the liquid crystal material and the photocurable resin in
order to prevents the generation of the disclination lines in these
elements. However, because the addition of the conventional polymeric
compounds enlarges the pretilt angle of the liquid crystal material in the
liquid crystal regions, the brightness of the element is reduced in the
absence of an electric voltage.
The present inventors have eagerly examined the relationship between the
structure of the polymeric compounds and the orientation of the liquid
crystal molecules in the interface between the liquid crystal material and
the polymer wall, and found a compound from which a liquid crystal display
element is obtained generating no disclination lines and also having
bright characteristics in the absence of an electric voltage.
SUMMARY OF THE INVENTION
The polymeric compound of this invention is represented by the following
general formula (I):
##STR4##
wherein A represents a hydrogen atom or
##STR5##
B represents a hydrogen atom or
##STR6##
each of X.sub.1 and X.sub.2 represents independently a hydrogen atom or a
methyl group, each of m and n represents independently an integer of 0 to
14, each of p and q represents independently 0 or 1, and each of Y.sub.1,
Y.sub.2, Y.sub.3, and Y.sub.4 represents independently a hydrogen atom or
a fluorine atom, with the proviso that both A and B are not hydrogen
atoms, p is 0 when m is 0, and q is 0 when n is 0.
In a preferred embodiment, in the general formula (I) A represents:
##STR7##
and B represents:
##STR8##
In a preferred embodiment, in the general formula (I) either A or B
represents a hydrogen atom.
In a preferred embodiment, in the general formula (I) A represents a
hydrogen atom or:
##STR9##
B represents a hydrogen atom or:
##STR10##
a preferred embodiment, in general formula (I) both p and q represent 1.
In a preferred embodiment, in the general formula (I) A represents:
##STR11##
and B represents a hydrogen atom. Alternatively, represents a hydrogen
atom and B represents:
##STR12##
In a preferred embodiment, in the general formula (I) at least one selected
from the group consisting of Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 is a
fluorine atom.
The liquid crystal display element of this invention comprises a pair of
substrates oppositely disposed through a gap, and a liquid crystal layer
placed in the gap. At least one of the substrates is transparent, and the
liquid crystal layer includes a liquid crystal region, and a polymer wall
surrounding the liquid crystal region, wherein the liquid crystal layer
includes a liquid crystal material, a polymeric polymer material, and the
above-described polymeric compound.
In a preferred embodiment, the liquid crystal region includes liquid
crystal molecules, and the orientation of the liquid crystal molecules is
either random, radial, concentric or spiral.
In a preferred embodiment, an alignment film is placed on the substrates.
In a preferred embodiment, the liquid crystal region includes liquid
crystal molecules, and the orientation of the liquid crystal molecules is
TN, STN, ECB or FLC.
In a preferred embodiment, the polymeric polymer material is a photocurable
resin.
In a preferred embodiment, the polymeric compound is represented by the
general formula (I), wherein either A or B represents a hydrogen atom.
In a preferred embodiment, the polymeric compound is represented by the
general formula (I), wherein A represents:
##STR13##
and B represents:
##STR14##
When a display mode utilizing an orientation restricting force on the
substrate is prepared from a mixture of a liquid crystal material and a
polymeric polymer material such as a photocurable resin, the orientation
restricting force of the alignment film to the liquid crystal molecules
generally tends to be weakened due to the formation of a polymer layer
consisting of the polymeric polymer material between the alignment film
and the liquid crystal region. However, when the polymeric compound of
this invention is contained in the polymer layer, an ability of
transferring the orientation restricting force of the alignment film to
the liquid crystal molecules inside the liquid crystal regions is also
created in the polymer layer to stabilize the orientation of the liquid
crystal molecules, due to the presence of a material having a structure
similar to the liquid crystal material in the polymer layer.
When the liquid crystal molecules present inside the liquid crystal region
are oriented symmetrical with respect to the axis (an axis which is at a
right angle to the surface of the substrate), disclination lines are
normally generated on the periphery of the liquid crystal region due to
the reverse tilt (See, FIG. 2) at the time of impressing an electric
voltage. However, because the addition of the polymeric compound of this
invention results in the generation of the pretilt of the liquid crystal
molecules on the substrate, the generation of the disclination lines is
controlled at the time of impressing an electric voltage which deteriorate
the black display level. Thus, the contrast of the display element is
dramatically improved.
Therefore, the invention described herein makes possible the advantages of
providing a liquid crystal display element which has the following
effects.
(1) Since the liquid crystal regions are surrounded by the polymer wall,
the gap is maintained between both substrates by the polymer wall.
Therefore, it is possible to control the deformation of the liquid crystal
display element against an external force, especially to control the
variation of its color which results when the surface of the element is
pressed by a pen.
(2) The conventional large screen liquid crystal display elements which are
placed vertically have different thicknesses in the upper and lower
portions due to the presence of gravity. This causes the unevenness of the
display. However, because the substrates of the liquid crystal display
element of this invention are attached throughout the whole surface of the
element, the thickness of the cell is not often varied.
(3) It is possible to make the orientation of the liquid crystal molecules
in the liquid crystal regions random, concentric, radial or spiral by
utilizing effectively the phase separation between the liquid crystal
material and the polymer wall consisting mainly of the polymeric polymer
materials at the time of curing the liquid crystal composition. Since the
liquid crystal of the liquid crystal regions is oriented symmetrically to
the axis, the liquid crystal display element thus obtained has excellent
viewing angle characteristics.
(4) It is possible to strengthen the orientation restricting force in the
interface between the liquid crystal material and the polymer layer by
using the polymeric compound of this invention.
(5) The liquid crystal display element of this invention is suitable for
personal display devices such as word processors, personal computers, and
the like; and devices used by a number of people (especially, those used
on a desk surrounded by 2-4 people) such as portable information end
devices, and the like.
These and other advantages of the present invention will become apparent to
those skilled in the art upon reading and understanding the following
detailed description with reference to the accompanying figures.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an enlarged view showing the liquid crystal region of the liquid
crystal display element of this invention;
FIG. 2 is a diagram showing the viewing angle characteristics of a TN mode
element;
FIG. 3 is a diagram showing the generation of the disclination lines at the
time of impressing an electric voltage;
FIG. 4 is an enlarged diagram showing the liquid crystal region using a
bifunctional polymeric compound;
FIG. 5 is a diagram of the photo-mask used in Example 9;
FIG. 6 is an enlarged diagram of the cell prepared in Example 9;
FIG. 7 is a series of graphs showing the electrooptical characteristics
(viewing angle characteristics) of the element prepared in Example 9; and
FIG. 8 is a series of graphs showing the electrooptical characteristics
(viewing angle characteristics) of a TN mode element.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The polymeric compound of this invention has a functional group reactive
with a polymeric polymer material, including monofunctional polymeric
compounds and polyfunctional polymeric compounds.
1. The monofunctional polymeric compounds
A. Structure
The monofunctional polymeric compound is a compound in which one polymeric
functional group is present in its molecule and bonded to a mesogen group
having liquid crystal properties.
B. Effects
The following illustrate the effects attained by the use of the polymeric
compound.
When a display mode utilizing an orientation restricting force on the
substrate is prepared from a mixture of a liquid crystal material and a
polymeric polymer material such as a photocurable resin, the orientation
restricting force of the alignment film to the liquid crystal molecules
generally tends to be weakened due to the formation of a polymer layer
consisting of the polymeric polymer material between the alignment film
and the liquid crystal region. However, when the polymeric compound of
this invention is contained in the polymer layer, an ability to transfer
the orientation restricting force of the alignment film to the liquid
crystal molecules inside the liquid crystal region is also created in the
polymer layer to stabilize the orientation of the liquid crystal
molecules. This is due to the presence of a material having a structure
similar to the liquid crystal material in the polymer layer.
When the liquid crystal molecules present inside the liquid crystal region
are oriented symmetrical with respect to the axis (the axis X which is
shown in FIG. 1(a) and is at a right angle of the surface of the
substrate), the disclination lines d are normally generated on the
periphery of the liquid crystal region due to the reverse tilt (See, FIG.
3) at the time of impressing an electric voltage. However, because the
addition of the polymeric compound of this invention results in the
generation of the pretilt of the liquid crystal molecules on the
substrate, the generation of the disclination lines is controlled at the
time of impressing an electric voltage (which is estimated to be due to
the fact that the liquid crystal molecules are oriented nearly at a right
angle at the time of impressing the electric voltage).
C. The influence derived from the variation of the chain length of the
linking groups in the polymeric compound
The numbers, n and m of the linking groups, --(CH.sub.2).sub.m
--or--(CH.sub.2).sub.n --which connect the mesogen group to the polymeric
functional group may influence the viewing angle characteristics of the
liquid crystal display element thus prepared.
In the above formula, m and n are 0 to 14, respectively. Preferably, m and
n are 0 or 3 to 14 and more preferably 4 to 7, respectively. If both m and
n are 2, the polymeric compound is too reactive to be practical. If both m
and n exceed 14, the mesogen portions appear on the surfaces of the
polymer wall and the polymer layer so that the response speed is reduced,
which is estimated to be due to the fact that the mesogen groups are
oriented in the same manner as the liquid crystal molecules. The longer
the chain length of the linking groups is, the smaller the amount of the
polymeric compound required to obtain an effect on controlling the
disclination lines. However, at the same time, the pretilt angle is
enlarged to reduce the transmittance of the cell. Thus, it is necessary to
select the amounts added and types of the polymeric compound so as to
control the disclination lines and also prevent the pretilt angle from
enlarging.
D. The effects of the fluorination of the polymeric compound on the viewing
angle characteristics of the element
There will be the following problems (a)-(d) arising in an element
comprising a liquid crystal layer having a liquid crystal region and a
polymer wall surrounding the liquid crystal region, the liquid crystal
region and the polymer wall being formed by the phase separation of a
mixture of a liquid crystal material and a polymeric polymer material by
the polymerization reaction.
Problems Estimated Causes
(a) Slow response speed--The dissolution of the polymer material, monomers
in the liquid crystal;
(b) The generation of hysteresis--The strong anchoring strength of the
liquid crystal molecules to the polymer wall;
(c) High driving voltage--The same as above item (b)
(d) The leakage of the light at the time of impressing a saturation
voltage--The dissolution of the liquid crystal molecules in the polymer
layer inside the liquid crystal region, and the strong anchoring strength
of the liquid crystal molecules to the polymer wall.
The causes of the above-described problems are due to the strong anchoring
strength of the liquid crystal molecules to the polymer wall, as well as
the good compatibility between the polymer material and the liquid crystal
material. Both of these problems may be solved by the use of a fluorinated
polymeric compound. Since the fluorinated polymeric compound is expected
to appear on the surfaces of the polymer wall and the polymer layer, the
orientation of the liquid crystal may be stabilized.
2. The polyfunctional polymeric compounds
A. Structure
The polyfunctional polymeric compound is a compound in which a plurality of
the polymerizable functional groups are bounded to the mesogen group
having liquid crystal properties. The number of the functional groups is
preferably 2. If it is 3 or more, the polymer wall is formed before the
liquid crystal region is largely developed due to the fact that the
gelation speed of the liquid crystal material becomes faster, and
therefore the transmittance of the liquid crystal display element thus
prepared is reduced in the absence of an electric voltage.
The numbers, n and m, of the linking groups --(CH.sub.2).sub.m -- or
--(CH.sub.2).sub.n -- which connect the above-described mesogen group to
the polymeric functional group are the same as those for the
above-described monofunctional polymeric compound, but are preferably 12
or less. If they exceed 12, the solubility of the polymeric compound in
the liquid crystal material is reduced.
B. Effects
Like the monofunctional polymeric compound, the polyfunctional polymeric
compound has an effect on stabilizing the orientation of the liquid
crystal molecules. Moreover, with respect to the generation of
disclination lines, the polyfunctional polymeric compound provides an
observed image which has a region having a smaller amount of twisting, as
is shown in FIG. 4, than obtained by the use of the monofunctional
polymeric compound, and generates no disclination lines at the time of
impressing an electric voltage.
The use of a fluoridized polyfunctional polymeric compound provides the
same effects as those of the monofunctional polymeric compound. In this
case, the site which is fluoridized may be located on the carbon inside
the mesogen backbone.
3. Retardation : d.multidot..DELTA.n , d: thickness of the liquid crystal
layer, .DELTA.n :birefringence
Since the liquid crystal molecules are nearly upright to the substrate
(when .DELTA..epsilon.>0) in the liquid crystal display element of this
invention having a polarizer at the time of impressing a saturation
voltage, (1) the polarizer has viewing angle characteristics, and (2) the
liquid crystal layer has retardation of d.multidot..DELTA.n. Therefore,
there is a region having poor viewing angle characteristics in the
direction of 45.degree. from the polarization axis of the polarizer.
The cause of the above-described problem (2) is that light entering from
the polarization direction of the polarizer has either an ordinary ray
only or an extraordinary ray only in crossing the refractive index
ellipsoid of the liquid crystal layer, and incident light entered in the
direction of 45.degree. from the polarization axis of the polarizer has
both an ordinary ray and an extraordinary ray in crossing the refractive
index ellipsoid of the liquid crystal layer. This causes leakage of the
light due to the generation of elliptic polarization. Thus, it is
preferred that the retardation of the liquid crystal layer be as small as
possible so that the elliptic polarization is not easily produced.
However, because the transmittance T.sub.0 in the absence of an electric
voltage is influenced by the retardation of the liquid crystal layer, it
is preferred in view of ensuring the omnidirectional properties of the
viewing angle characteristics and the brightness of the cell that the
retardation of the liquid crystal layer be 300 nm to 650 nm. If the
retardation is less than 300 nm, the cell shows a dark display due to the
lack of the brightness in the absence of an electric voltage. It is
preferred that the twist angle be 45.degree. to 150.degree., and
especially be in the neighborhood of 90.degree. which satisfies the first
minimum conditions because the cell has the highest brightness at this
angle.
4. Liquid crystal display elements
The liquid crystal display element of this invention comprises two
substrates 1a and 1b, both of which are oppositely placed with a gap
therebetween, and a liquid crystal layer 2 placed inside the gap, as shown
in FIG. 1. At least one of the two substrates 1a and 1b may be
transparent. The liquid crystal layer 2 has a number of liquid crystal
regions 20, and a polymer wall 21 surrounding the liquid crystal regions
20. An exemplary, liquid crystal display element is prepared as follows.
Two substrates in which transparent electrodes are provided are placed with
a gap therebetween by the use of a spacer to form a cell. On one side of
the cell, a photo-mask 3 is disposed as shown in FIG. 5. A liquid crystal
composition containing a liquid crystal material, a polymeric polymer
material, and at least one of the above-described polymeric compounds is
injected into the cell. Then, the cell is irradiated with ultraviolet ray
on the photo-mask side while impressing an electric voltage between the
transparent electrodes. The polymeric polymer material and polymeric
compounds in the liquid crystal composition in the cell are polymerized
and cured by the irradiation of the ultraviolet ray. In the process of the
polymerization, the phases of the liquid crystal material and the
polymeric polymer material in the liquid crystal composition are separated
to form liquid crystal regions 20 surrounded by polymer walls consisting
of the polymeric polymer material and the polymeric compounds in portions
30 which correspond to the above-described photo-mask, as shown in FIG. 6.
Polymeric polymer materials which can be used in the above-described
display element include known polymerizable resins which are preferably
photocurable resins.
These photocurable resins include, for example, acrylic acids and acrylates
having a long chain alkyl group of 3 or more carbons or a benzene ring,
including isobutyl acrylate, stearyl acrylate, lauryl acrylate, isoamyl
acrylate, n-butyl methacrylate, n-lauryl methacrylate, tridecyl
methacrylate, 2-ethylhexyl acrylate, n-stearyl methacrylate, cyclohexyl
methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl
acrylate, isobornyl methacrylate, and the like. The photocurable resins
also include polyfunctional resins to increase the physical strength of
the polymer material such as bisphenol A dimethacrylate, bisphenol A
diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate,
trimethylolpropane trimethacrylate, trimethylolpropane triacrylate,
tetramethylolmethane tetracrylate, neopentyl diacrylate, and the like.
5. Driving methods
The liquid crystal display element thus prepared may be driven by a driving
method such as simple matrix driving and active driving method including
for example a--Si TFT, p--Si TFT, MIM, and the like, but the driving
method is not particularly limited in the present invention.
6. Substrate materials
The substrate materials that can be used in the present invention include
glass plates, plastic plates, and the like which are made from transparent
solids, and substrates with a thin metal film, Si substrates, and the like
which are made from non-transparent solids. The substrates with a thin
metal film are effective for a reflection type liquid crystal display
element.
The plastic substrate is preferably made from a material which does not
absorb visible light, including for example PET, acrylic polymers,
polystyrenes, polycarbonates, and the like. Also, when the plastic
substrate is used, the polarization ability may be imparted to the
substrate itself.
Moreover, a laminated substrate made by combining two types of different
substrates, or a laminated substrate made by combining two substrates of
either the same or different types having different thicknesses may also
be used.
The following illustrate the outline of a method for synthesizing the
above-described polymeric compound. The following synthesis routes are
illustrative examples, and the present invention is not limited to these
examples.
7. Synthesis routes
Synthesis route 1: The compound represented by the general formula (I);
##STR15##
(Note) The symbol, MOM indicates CH.sub.3 OCH.sub.2 -group Synthesis route
2: The compound represented by the general formula (I), wherein A and B
are the same group;
##STR16##
Synthesis route 3: The compound represented by the general formula (I),
wherein either A or B is hydrogen atom;
##STR17##
Synthesis route 4: The synthesis of the intermediate compound;
##STR18##
The following outline the synthesis routes 1-4.
Synthesis route 1:
The compounds represented by the general formulae (1), (4), (5), (6), (7)
and (8) are commercially available. Also, the compound represented by the
general formula (3), where each of Y.sub.1 and Y.sub.2 is a hydrogen atom
or a fluorine atom is also commercially available.
The compound represented by the general formula (1) is reacted with C.sub.4
H.sub.9 Li and thereafter with B(OCH.sub.3).sub.3, and hydrolyzed to
obtain the compound represented by the general formula (2) which is then
oxidized using hydrogen peroxide to obtain the compound represented by the
general formula (3).
The compound represented by the general formula (3) is etherified with the
compound represented by the general formula (8) to obtain the compound
represented by the general formula (16) which is then esterified with the
compound represented by the general formula (7), or the compound
represented by the general formula (3) is directly esterified with the
compound represented by the general formula (7) to obtain the compound
represented by the general formula (17).
The compound represented by the general formula (4) is etherified with
methoxymethyl chloride (MOM-Cl) to obtain the compound represented by the
general formula (13) which is then reacted with C.sub.4 H.sub.9 Li and
thereafter with B(OCH.sub.3).sub.3, and hydrolyzed to obtain the compound
represented by the general formula (15). Also, the compound represented by
the general formula (5) is etherified with MOM-Cl to obtain the compound
represented by the general formula (14) which is then reacted with
magnesium (Mg) to form a Grignard reagent. The compound represented by the
general formula (15) may also be obtained by reacting the Grignard reagent
with B(OCH.sub.3).sub.3.
The compound represented by the general formula (17) which is obtained by
the above-described procedure is coupled with the compound represented by
the general formula (15) in the presence of a palladium (Pd) catalyst to
obtain the compound represented by the general formula (18).
The methoxymethyl (MOM) group of the compound represented by the general
formula (18) is eliminated under the acidic conditions to obtain the
compound represented by the general formula (19) which is then esterified
or etherified with the compound represented by the general formula (8), or
the compound represented by the general formula (12) (Synthesis route 4),
respectively to obtain the compound represented by the general formula
(I).
Synthesis route 2:
The compound represented by the general formula (20) which is obtained by
etherifying the compound represented by the general formula (3) with
MOM-Cl is coupled with the compound represented by the general formula
(15) which is obtained in the above-described synthesis route 1 in the
presence of a Pd catalyst to obtain the compound represented by the
general formula (21).
The MOM Group of the compound represented by the general formula (21) is
eliminated under the acidic conditions to obtain the compound represented
by the general formula (22). The compound represented by the general
formula (22) is esterified or etherified with the compound represented by
the general formula (7) or the compound represented by the general formula
(11) (Synthesis route 4), respectively to obtain the compound represented
by the General formula (I), wherein A and B are the same group.
Synthesis route 3:
The compound represented by the general formula (1) is coupled with the
compound represented by the general formula (15) in the presence of a Pd
catalyst to obtain the compound represented by the general formula (23).
The MOM group of the compound represented by the general formula (23) is
eliminated under the acidic conditions to obtain the compound represented
by the general formula (24).
The compound represented by the general formula (24) is esterified or
etherified with the compound represented by the general formula (8) or the
compound represented by the general formula (12), respectively, to obtain
the compound represented by the general formula (I), wherein either A or B
is a hydrogen atom.
Synthesis route 4:
The commercially available compound represented by the general formula (9)
is esterified with the compound represented by the general formula (7) to
obtain the compound represented by the general formula (11) Also, the
compound represented by the general formula (10) is esterified by the
compound represented by the general formula (8) to obtain the compound
represented by the general formula (12).
EXAMPLES
The following are illustrative examples of the present invention. However,
the present invention is not intended to be limited to these examples.
Additionally, the abbreviations described in the present examples indicate
the following:
GC; Gas chromatography
HPLC; High-performance liquid chromatography
TLC; Thin layer chromatography
IR; Infrared absorption spectrum
Mass; Mass spectrum
b.p.; Boiling point
m.p.; Melting point
GTO; Glass tube oven
Y; Yield
Example 1
(a) The synthesis of
##STR19##
Into a reactor, 40 g of p-bromophenol and 200 ml of DMF (dimethylformamide)
were charged, to which 10 g of a 60% NaH (sodium hydride) were gradually
added to give a solution. To the solution, 18 g of methoxymethyl chloride
were added dropwise with stirring at a temperature of 30.degree. C. or
lower, and reacted overnight at room temperature to give a reaction
solution. The reaction solution was poured into water, extracted with
benzene, washed with water, dried over sodium sulfate anhydride, and
thereafter the solvent was evaporated and the residue was distilled under
reduced pressure to give 38.4 g (Y., 79.3%) of 4-bromopheny methoxymethyl
ether.
b.p.; 65.degree.-67.degree. C./0.6 mmHg
GC; 99.4%
(b) The synthesis of
##STR20##
Into a reactor, 100 g of 1,2-difluorobenzene and 350 ml of THF
(tetrahydrofuran) were charged under an argon stream, to which 700 ml of a
1.6M C.sub.4 H.sub.9 Li (butyl lithium)/hexane solution were added
dropwise with stirring at a temperature of -50.degree. C. to -60.degree.
C. and stirred at the same temperature for 1 hour to give a solution.
Thereafter, 175 g of (CH.sub.3 O).sub.3 B (trimethyl borate) were added
dropwise, and stirred at the same temperature for 1 hour.
The mixture was stirred overnight while reducing the temperature gradually
to room temperature. Thereafter, the mixture was cooled to 0.degree. C.,
to which a dilute hydrochloric acid was added to give a reaction solution.
The reaction solution was extracted with toluene, washed with water, dried
over sodium sulfate anhydride, and thereafter the solvent was evaporated
and the crystallized residue was immersed into and washed with hot hexane
to give 80.8 g (Y., 56.6%) of 2,3-difluorophenyl boronic acid.
HPLC; 99.5%
(c) The synthesis of
##STR21##
Into a reactor, 5.1 g of Pd(PPh.sub.3).sub.4 (tetrakistriphenylphosphine
palladium), 210 ml of a benzene solution of 33 g of 4-bromopheny
methoxymethyl ether obtained in the above-described synthesis (a), 135 ml
of a 2M aqueous solution of Na.sub.2 CO.sub.3, and 120 ml of an ethanol
solution of 24 g of 2,3-difluorophenyl boronic acid obtained in the
above-described synthesis (b) were charged under an argon stream, and
stirred for 6 hours under reflux condition to give a reaction solution.
The reaction solution was poured into water, extracted with toluene,
washed with water, dried over sodium sulfate anhydride, and thereafter the
solvent was evaporated and the residue was distilled under reduced
pressure to give 20.1 g (Y., 53.6%) of
2,3-difluoro-4'-(methoxymethyl)biphenyl.
b.p.; 110.degree.-120.degree. C./0.25 mmHg
GC; 96.0%
(d) The synthesis of
##STR22##
Into a reactor, 20.1 g of 2,3-difluoro-4'-(methoxymethyl)biphenyl obtained
in the above-described synthesis (c), 60 ml of THF, and 90 ml of a 6N-HCl
were charged, and stirred for 3 hours under reflux condition to give a
reaction solution. The reaction solution was cooled, and thereafter
extracted with toluene, washed with water, dried over sodium sulfate
anhydride, and the solvent was evaporated and the residue was distilled
under reduced pressure to give 9.0 g (Y., 54.3%) of
2,3-difluoro-4'-hydroxybiphenyl.
b.p.; .160.degree.-170.degree. C./18 mmHg
m.p.; 132.degree.-134.4.degree. C.
GC; 99.7%
(e) The synthesis of
##STR23##
Into a reactor, 4.0 g of 2,3-difluoro-4'-hydroxybiphenyl obtained in the
above-described synthesis (d), 2.0 g of triethylamine, and 300 ml of
benzene were charged, to which a solution of 1.9 g of acryloyl chloride in
100 ml of benzene was added dropwise, and stirred for 5 hours to give a
reaction solution. The reaction solution was washed with a 3N-hydrochloric
acid and then with water, and thereafter dried over sodium sulfate
anhydride, and the solvent was evaporated and the residue was purified by
the silica gel column chromatography (eluent; toluene), and then
recrystalized from hexane to give 4.5 g (Y., 88.5%) of
2,3-difluorobiphenyl-4'-yl acrylate.
m.p.; 88.4.degree.-90.0.degree. C.
The purity of this material was 99.2% measured by GC, 99.5% measured by
HPLC, and 1 spot measured by TLC. Also, according to the results of the IR
measurement, the fact that a molecular ion peak was observed in 260 by the
Mass analysis, and the types of the starting materials used, the resulting
material was identified as a marked material.
Example 2
(a) The synthesis of CH.sub.2 .dbd.CHCOO(CH.sub.2).sub.6 Br
Into a reactor, 30 g of 6-bromo-1-hexanol, 18.4 g of triethylamine, and 500
ml of benzene were charged, to which a solution of 16.5 g of acryloyl
chloride in 200 ml of benzene was added dropwise, while stirring and
cooling with ice, and stirred for 3 hours to give a reaction solution. The
reaction solution was washed with a 3N-HCl and then with water, dried over
sodium sulfate anhydride, and thereafter the solvent was evaporated and
the residue was purified by the silica gel column chromatography (eluent;
toluene) to give 25.4 g (Y., 65.1%) of 6-bromohexyl acrylate.
GC; 95.9%
(b) The synthesis of
##STR24##
Into a reactor, 4 g of 2,3-difluoro-4'-hydroxybiphenyly obtained in the
above-described synthesis (d) of Example 1, 5.0 g of 6-bromohexyl acrylate
obtained in the above-described synthesis (a), 5.4 g of K.sub.2 CO.sub.3
and 400 ml of 2-butanone were charged, and further stirred and refluxed
for 28 hours to give a reaction solution.
The reaction solution was poured into water, extracted with toluene, washed
with water, dried over sodium sulfate anhydride, and thereafter the
solvent was evaporated and the residue was purified by the silica gel
column chromatography (eluent; toluene), and then recrystallized twice
from hexane to give 5.35 g (Y., 76.5%) of
2,3-difluoro-4'-›6-(acryloyloxy)hexyloxy!biphenyl.
m.p.; 45.6.degree.-46.8.degree. C.
The purity of this material was 99.0% measured by GC, 99.0% measured by
HPLC, and 1 spot measured by TLC. Also, according to the results of the IR
measurement, the fact that a molecular ion peak was observed in 360 by the
Mass analysis, and the types of the starting materials used, the resulting
material was identified as a marked material.
Example 3
(a) The synthesis of CH.sub.2 .dbd.CHCOO(CH.sub.2).sub.12 Br
The same procedure as in the synthesis (a) of Example 2 was repeated except
that 44.0 g of 12-bromo-1-dodecanol were used instead of 30 g of
6-bromo-1-hexanol to give 39.8 g (Y., 75.1%) of 12-bromododecyl acrylate.
(b) The synthesis of
##STR25##
The same procedure as in the synthesis (b) of Example 2 was repeated except
that 6.7 g of 12-bromododecyl acrylate were used instead of 5.0 g of
6-bromohexyl acrylate to give 2.1 g (Y., 24.1%) of
2,3-difluoro-4'-›12-(acryloyloxy)dodecyloxy!biphenyl. m.p.;
59.7.degree.-60.7.degree. C.
The purity of this material was 99.4% measured by HPLC, and 1 spot measured
by TLC. Also, according to the results of the IR measurement, the fact
that a molecular ion peak was observed in 444 by Mass analysis, and the
types of the starting materials used, the resulting material was
identified as a marked material.
Example 4
(a) The synthesis of
##STR26##
In a reactor, 10.0 g of 4-bromophenol, 7.95 g of ethylene bromohydrin, 16.0
g of K.sub.2 CO.sub.3, and 300 ml of acetone were charged, and stirred and
refluxed for 50 hours to give a reaction solution. The reaction solution
was poured into water, extracted with toluene, washed with water, and
thereafter dried over sodium sulfate anhydride, and the solvent was
evaporated and the residue was distilled under reduced pressure in GTO
(glass tube oven) to give 5.55 g (Y., 44.3%) of
1-bromo-4-(2-hydroxyethoxy) benzene.
GC; 96.8%
b.p.; 100.degree. C./0.1 mmHg (which was the prescribed temperature of GTO)
(b) The synthesis of
##STR27##
Into a reactor, a solution of 5.0 g of 4-(2-hydroxyethyl)oxy-bromobenzene
in 150 ml of benzene, 7.2 g of 2,3-difluorophenyl boronic acid obtained in
the synthesis (b) of Example 1, 68 ml of a 2M aqueous solution of Na.sub.2
CO.sub.3, and 1.0 g of Pd(PPh.sub.3).sub.4 were charged, and stirred and
refluxed for 9 hours to give a reaction solution. The reaction solution
was poured into water, extracted with toluene, washed with water, dried
over sodium sulfate anhydride, and thereafter the solvent was evaporated
and the residue was distilled under reduced pressure in GTO, and
recrystallized from an ethanol/hexane (=1/1) mixed solvent to give 4.2 g
(Y., 72.7%) of 2,3-difluoro-4'-(2-hydroxyethoxy)biphenyl.
(c) The synthesis of
##STR28##
Into a reactor, 2.0 g of 2,3-difluoro-4'-(2-hydroxyethoxy)biphenyl obtained
in the above-described synthesis (b), 0.9 g of triethylamine, and 300 ml
of diethylether were charged, to which a solution of 0.8 g of acryloyl
chloride in 100 ml of diethylether was added dropwise, while stirring and
cooling with ice, and stirred for 4 hours to give a reaction solution. The
reaction solution was washed with a dilute hydrochloric acid and then with
water, dried over sodium sulfate anhydride, and thereafter the solvent was
evaporated and the residue was purified by the silica gel column
chromatography (eluent; toluene) to give 0.72 g (Y., 29.6%) of
2,3-difluoro-4'-›2-(acryloyloxy)ethoxy!biphenyl.
m.p.; 47.4.degree.-50.1.degree. C.
The purity of this material was 99.4% measured by HPLC, and 1 spot measured
by TLC. Also, according to the results of the IR measurement, the fact
that a molecular ion peak was observed in 304 by the Mass analysis, and
the types of the starting materials used, the resulting material was
identified as a marked material.
Example 5
(a) The synthesis of
##STR29##
Into a reactor, 2.1 g of Pd(PPh.sub.3).sub.4, a solution of 11.6 g of
1-bromo-2,3-difluorobenzene in 100 ml of benzene, 60 ml of a 2M aqueous
solution of Na.sub.2 CO.sub.3, and a solution of 13.3 g of
2,3-difluorophenyl boronic acid obtained in the synthesis (b) of Example 1
in 100 ml of ethanol were charged under an argon stream, and stirred for 6
hours under reflux condition to give a reaction solution. The reaction
solution was washed with a dilute hydrochloric acid and then with water,
dried over sodium sulfate anhydride, and the solvent was evaporated and
the residue was distilled under reduced pressure to give 5.7 g (Y., 42%)
of 2,2',3,3'-tetrafluorobiphenyl.
(b) The synthesis of
##STR30##
Into a reactor, 5.7 g of 2,2',3,3'-tetrafluorobiphenyl obtained in the
above-described synthesis (a), and 50 ml of THF were charged under an
argon stream, to which 38 ml of a 1.6M C.sub.4 H.sub.9 Li/hexane solution
were added dropwise at a temperature of -50.degree. C. or lower, and
stirred at the same temperature for 2 hours, to which 10 g of (CH.sub.3
O).sub.3 B (trimethyl borate) were added dropwise, and heated gradually to
room temperature, and stirred overnight.
To the reactor, a dilute sulfuric acid was added and stirred for 1 hour,
and thereafter extracted with an ether, washed with water, dried over
sodium sulfate anhydride, and the solvent was evaporated and recover the
residue. To the residue, hexane was added, and then immersed and washed to
give a crystal, to which 50 ml of THF were added to dissolve, followed by
the addition of 40 ml of a 10% aqueous H.sub.2 O.sub.2 solution. This
mixture was then stirred overnight at room temperature to give a reaction
solution. The reaction solution was extracted by the addition of toluene,
washed with water, dehydrated with sodium sulfate anhydride, and
thereafter the solvent was evaporated and recover the residue (4.3 g of
the crude 2,2',3,3'-tetrafluoro-4,4'-dihydroxybiphenyl).
GC; 92%
(c) The synthesis of CH.sub.2 .dbd.CHOO(CH.sub.2).sub.8 Br
The same procedure as in the synthesis (a) of Example 2 was repeated except
that 34.7 g of 8-bromo-1-octanol were used instead of 30 g of
6-bromo-1-hexanol to give 34.1 g (Y., 78%) of 8-acryloyloxy-1-bromooctane.
GC; 97%
(d) The synthesis of
##STR31##
Into a reactor, 4.3 g of the crude
2,2',3,3'-tetrafluoro-4,4'-dihydroxybiphenyl obtained in the
above-described synthesis (b), 10.0 g of 8-acryloyloxy-1-bromooctane
obtained in the above-described synthesis (c), 7.8 g of K.sub.2 CO.sub.3,
and 30 ml of acetone were charged, and refluxed and stirred for 16 hours
to give a reaction solution.
The reaction solution was filtered through a filter aid (Highflow) to give
a filtrate, to which toluene was added, and washed with water, dried over
sodium sulfate anhydride, and thereafter the solvent was evaporated and
the residue was purified twice by the silica gel column chromatography
(eluent; toluene/ethyl acetate=20/1), and then recrystallized from acetone
to give 1.28 g (Y,. 12.9%) of
4,4'-bis›8-(acryloyloxy)octyloxy!-2,2',3,3'-tetrafluorobiphenyl.
m.p.; 60.5.degree.-61.4.degree. C.
The purity of this material was 99.7% measured by HPLC, and 1 spot measured
by TLC. Also, according to the results of the IR measurement, the fact
that a molecular ion peak was observed in 622 by Mass analysis, and the
types of the starting materials used, the resulting material was
identified as a marked material.
Example 6
(a) The synthesis of
##STR32##
The same procedure as in the synthesis (a) of Example 1 was repeated except
that 30 g of 2,3-difluorophenol were used instead of 40 g of p-bromophenol
to give 32.6 g (Y., of 81.4%) methoxymethyl-2,3-difluorophenyl ether.
GC; 99.6%
b.p.; 82.degree.-84.degree. C./14 mmHg
(b) The synthesis of
##STR33##
The same procedure as in the synthesis (b) of Example 1 was repeated except
that 152.2 g of methoxymethyl-2,3-difluorophenyl ether obtained in the
above-described synthesis (a) were used instead of 100 g of
1,2-difluorobenzene to give 150.6 g (Y., 78.8%) of
2,3-difluoro-4-(methoxymethoxy)phenyl boronic acid.
HPLC; 97.4%
(c) The synthesis of
##STR34##
The same procedure as in the synthesis (c) of Example 1 was repeated except
that 32.7 g of 2,3-difluoro-4-(methoxymethyl)oxyphenyl boronic acid
obtained in the above-described synthesis (b) were used instead of 24 g of
2,3-difluorophenyl boronic acid to give 23.4 g (Y., 95.0%) of
2,3-difluoro-4,4'-bis(methoxymethoxy)biphenyl.
GC; 96%
(d) The synthesis of
##STR35##
The same procedure as in the synthesis (d) of Example 1 was repeated up to
the distillation step of the solvent except that 24.2 g. of
2,3-difluoro-4,4'-bis(methoxymethoxy)-biphenyl obtained in the
above-described synthesis (c) were used instead of 20.1 g of
2,3-difluoro-4'-(methoxymethoxy)biphenyl to give 17 g of the residue (the
crude 2,3-difluoro-4,4'-dihydroxybiphenyl).
(e) The synthesis of
##STR36##
The same procedure as in the synthesis (d) of Example 1 was repeated except
that 3.6 g of the crude 2,3-difluoro-4,4'-dihydroxybiphenyl obtained in
the above-described synthesis (d) were used instead of 4.3 g of
2,2',3,3'-tetrafluoro-4,4'-dihydroxybiphenyl to give 1.0 g (Y., 10.5%) of
4,4'-bis›8(acryloyloxy)octyloxy!-2,3-difluorobiphenyl.
m.p.; liquid at room temperature
The purity of this material was 99.0% measured by HPLC, and 1 spot measured
by TLC. Also, according to the results of the IR measurement, the fact
that the molecular ion peak was observed in 586 by the Mass analysis, and
the types of the starting materials used, the resulting material was
identified as a marked material.
Example 7
(a) The synthesis of
##STR37##
The same procedure as in the synthesis (a) of Example 1 was repeated except
that 43.9 g of 2-fluoro-4-bromophenol were used instead of 40 g of
p-bromophenol to give 46.7 g (Y., 86.4%) of methoxymethy
4-bromo-2-fluorophenyl ether.
GC; 97.2%
b.p.; 118.degree.-120.degree. C./14 mmHg
(b) The synthesis of
##STR38##
Into a reactor, 8 g of Mg, and a small number of iodine pieces were
charged, to which a solution of 66 g of methoxymethy
4-bromo-2-fluorophenyl ether obtained in the above-described synthesis (a)
in 300 ml of THF was added dropwise (if necessary, heated) in a small
amount to commence the reaction. Thereafter, the remaining THF solution
was added dropwise to the reactor while stirring and refluxing. After the
termination of the dropwise addition, the solution was further stirred and
refluxed for 4 hours to prepare a Grignard reagent.
Into the other reactor, 54 g of (CH.sub.3 O).sub.3 B and 200 ml of THF were
charged, to which the Grignard reagent previously prepared was added
dropwise while stirring at a temperature of 0.degree. C. or lower, and
gradually heated to room temperature, and thereafter stirred overnight to
give a reaction solution. The reaction solution was poured into a dilute
sulfuric acid, extracted with an ether, washed with a cold water, dried
over sodium sulfate anhydride, and the solvent was evaporated and the
residue was immersed into and washed with hexane to give 47.2 g (Y.,
84.0%) of 3-fluoro-4-(methoxymethoxy)phenyl boronic acid.
HPLC; 88.8%
(c) The synthesis of
##STR39##
The same procedure as in the synthesis (c) of Example 1 was repeated except
that 30 g of 3-fluoro-4-(methoxymethoxy)phenyl boronic acid obtained in
the above-described synthesis (b) were used instead of 24 g of
2,3-difluorophenyl boronic acid, and 35.3 g of methoxymethyl
4-bromo-2-fluorophenyl ether obtained in the above-described synthesis (a)
were used instead of 33 g of methoxymethyl-4-bromophenylether to give 31.9
g (Y., 68.7%) of 3,3'-difluoro-4,4'-bis(methoxymethoxy)biphenyl.
GC; 99%
m.p. 76.3.degree.-77.3.degree. C.
(d) The synthesis of
##STR40##
The same procedure as in the synthesis (d) of Example 1 was repeated except
that 24 g of 3,3'-difluoro-4,4'-bis(methoxymethoxy)biphenyl obtained in
the above-described synthesis (c) were used instead of 20.1 g of
2,3-difluoro-4'-(methoxymethoxy)biphenyl to give 17.0 g (Y., 98%) of the
crude 3,3'-difluoro-4,4'-dihydroxybiphenyl.
GC; 99.6%
(e) The synthesis of
##STR41##
The same procedure as in the synthesis (d) of Example 5 was repeated except
that 3.6 g of the crude 3,3'-difluoro-4,4'-dihydroxybiphenyl obtained in
the above-described synthesis (d) were used instead of 4.3 g of
2,2',3,3'-tetrafluoro-4,4'-dihydroxybiphenyl to give 0.34 g (Y., 3.6%) of
3,3'-difluoro-4,4'-bis›8-(acryloyloxy) octyloxy!biphenyl.
m.p.; 56.1.degree.-57.9.degree. C.
The purity of this material was 99.5% measured by HPLC, and 1 spot measured
by TLC. Also, according to the results of the IR measurement, the fact
that a molecular ion peak was observed in 586 by the Mass analysis, and
the types of the starting materials used, the resulting material was
identified as the marked material.
Example 8
(a) The synthesis of
##STR42##
The same procedure as in the synthesis (c) of Example 1 was repeated except
that 32.7 g of 2,3-difluoro-4-(methoxymethoxy)phenyl boronic acid obtained
in the synthesis (b) of Example 6 were used instead of 24 g of
2,3-difluorophenyl boronic acid, and 35.7 g of methoxymethyl
4-bromo-2-fluorophenyl ether obtained in the synthesis (a) of Example 7
were used instead of 33 g of methoxymethyl 4-bromophenyl ether to give
20.5 g (Y., 50%) of 2,3,3'-trifluoro-4,4'-bis(methoxymethoxy)biphenyl.
GC; 95%
(b) The synthesis of
##STR43##
The same procedure as in the synthesis (d) of Example 1 was repeated up to
the distillation step of the solvent except that 21.7 g of
2,3,3'-trifluoro-4,4'-bis(methoxymethoxy)biphenyl obtained in the
above-described synthesis (a) were used instead of 20.1 g of
2,3-difluoro-4'-(methoxymethoxy)biphenyl to give 14.7 g of the crude
2,3,3'-trifluoro-4,4'-dihydroxybiphenyl.
(c) The synthesis of
##STR44##
The same procedure as in the synthesis (d) of Example 5 was repeated except
that 3.4 g of the crude 2,3,3'-trifluoro-4,4'-dihydroxybiphenyl obtained
in the above-described synthesis (b) were used instead of 4.3 g of
2,2',3,3'-tetrafluoro-4,4'-dihydroxybiphenyl to give 9 g (Y., 90%) of
2,3,3'-trifluoro-4,4'-bis›8-(acryloyloxy)octyloxy!biphenyl.
m.p.; liquid at room temperature
The purity of this material was 99% measured by HPLC, and 1 spot measured
by TLC. Also, according to the results of the IR measurement, the fact
that a molecular ion peak was observed in 604 by the Mass analysis, and
the types of the starting materials used, the resulting material was
identified as a marked material.
Examples 9-13
(The liquid crystal display elements using a monofunctional liquid crystal
polymeric material)
A cell was prepared using 1.1 mm glass substrates having ITO (a mixture of
indium oxide and tin oxide; having a thickness of 500 angstrom)
transparent electrodes while maintaining a 5 .mu.m gap with a spacer. On
one side of the cell thus prepared, the photo-mask 3 was disposed as shown
in FIG. 5. Moreover, a uniform mixture of 0.65 g of stearyl acrylate, 0.15
g of 1,4-butanediol acrylate, 0.10 g of styrene, 0.10 g of the polymeric
compound X shown in Table 1, 13.3 g of a liquid crystal material, ZLI-4792
(manufactured by Merck, Inc.; .DELTA.n=0.094), and 0.04 g of a
photoinitiator (Irgacure 651) was injected into the cell by a capillary
tube.
TABLE 1
______________________________________
Compound X Value of n
Example No.
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##STR45## 12 6 4 8 9 10 11 12
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Then, while impressing a .+-.4V electric voltage between the transparent
electrodes, the cell was irradiated with a parallel light from a high
pressure mercury lamp at a rate of 10 mW/cm.sup.2 at 100.degree. C. for 8
minutes (The ultraviolet ray was irradiated to create a spatially regular
pattern to the cell).
Then, the cell was gradually cooled to 25.degree. C. (at which the liquid
crystal was in a nematic state) at a rate of 10.degree. C./hr. while
impressing an electric voltage, and further irradiated continuously with
the ultraviolet ray for 3 minutes to cure the resin to prepare a liquid
crystal display element.
When the resulting element was observed by a polarization microscope, it
was observed that the liquid crystal regions 20 were formed in the
portions corresponding to the photo-mask and that the liquid crystal
molecules were spirally oriented around a central axis which was located
in the center of the liquid crystal region, as shown in FIG. 6. A
polarizing plate was attached to each substrate of the cell so that they
were at a right angle to each other. FIG. 7 shows the electrooptical
characteristics of the cell obtained in Example 11. The electrooptical
characteristics of the cells obtained in other examples (Examples 9, 10,
12 and 13) generally showed the same trend as those shown in FIG. 7.
The generation of disclination lines was substantially perfectly controlled
in the cells of Examples 9-11, but a few disclination lines were generated
in the cells of Examples 12 and 13. The transmittance of the cell of
Example 9 in the absence of an electric voltage was significantly reduced
as illustrated in Table 2. The higher the number of n in the general
formula (I), the larger the transmittance of the cell.
TABLE 2
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Exam- Exam- Exam- Exam- Exam-
ple 9 ple 10 ple 11 ple 12 ple 13
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Transmittance in
37 48 51 55 52
the absence of an
electric voltage (%)
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Examples 14-17
(The liquid crystal display elements using a bifunctional liquid crystal
polymeric material)
On a cell prepared by the same procedure as in Examples 9-13, a photo-mask
was disposed in the same manner as in Examples 9-13. Moreover, a uniform
mixture of 0.75 g of stearyl acrylate, 0.10 g of styrene, 0.15 g of the
polymeric compound Y shown in Table 3, 13.3 g of a liquid crystal
material, ZLI-4792 (manufactured by Merck, Inc.; .DELTA.n=0.094), and 0.04
g of a photoinitiator (Irgacure 651) was injected into the cell by a
capillary tube.
TABLE 3
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Value
Compound Y of n Example No.
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##STR46## 12 8 6
13 14 15
##STR47## 8 16
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The cell into which the mixture was injected was irradiated with an
ultraviolet ray while impressing an electric voltage in the same manner as
in Examples 9-13 to prepare a liquid crystal display element.
When the element thus prepared was observed by a polarization microscope,
it was observed that the liquid crystal regions 20 were formed in the
portions corresponding to the photo-mask, that the liquid crystal
molecules were spirally oriented around a central axis which was located
in the center of the liquid crystal region, end that regions having a
smaller amount of twisting were formed in the neighborhood of the liquid
crystal regions, as shown in FIG. 4. When a polarizing plate was attached
to each substrate of the cell so that they were at a right angle to each
other, it was observed that the same viewing angle characteristics as
those of Examples 9-13 were obtained.
Moreover, when an electric voltage was impressed on the resulting element,
the generation of disclination lines was not observed in the element.
Table 4 illustrates the electrooptical characteristics of the element thus
prepared.
TABLE 4
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Example Example Example Example
14 15 16 17
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Transmittance
36 53 50 52
in the absence of
an electic voltage (%)
Transmittance
0.9 0.8 0.8 0.6
when a voltage of
10 V is applied (%)
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According to Table 4, the cell of Example 17, which was prepared from the
fluoridized bifunctional liquid crystal polymer material, has a lower
transmittance at the time of impressing an electric voltage, and exhibits
excellent display characteristics. This is because (1) the cell of Example
17 provides more double refractions of the remaining liquid crystal
materials than the cells of Examples 9-13, and (2) the liquid crystal
molecules were not easily dissolved in the polymer film attached on the
substrates by using the fluoridized liquid crystal material, thereby
reducing an anchoring strength to the surface of the polymer film, as
observed with the polarization microscope.
Comparative Example 1
On the cell prepared in Example 9, a photo-mask 3 was disposed as shown in
FIG. 5. Moreover, a uniform mixture of 0.75 g of stearyl acrylate, 0.15 g
of 1,4-butanediol acrylate, 0.10 g of styrene, 13.3 g of a liquid crystal
material, ZLI-4792 (manufactured by Merck, Inc.; .DELTA.n=0.094), and 0.04
g of a photoinitiator (Irgacure 651) was injected into the cell by a
capillary tube.
Then, the cell was irradiated with an ultraviolet ray, while impressing an
electric voltage in the same manner as in Examples 9-13 to prepare a
liquid crystal display element.
When an electric voltage was impressed on the element thus prepared, the
generation of disclination lines was observed by a polarization
microscope. Moreover, the transmittance of the cell at the time of
impressing an electric voltage was 2.2%. Since this value was greater than
those of the cells of Examples 14-17, it was believed that the increase of
the transmittance is due to the generation of disclination lines.
Example 18
A polyimide film (AL4552; manufactured by Nihon Synthetic Rubber, Inc.) was
applied to 1.1 mm glass substrates having ITO (a mixture of indium oxide
and tin oxide; having a thickness of 500 angstrom) transparent electrodes
formed by the spin coating method, and subjected to the rubbing treatment
with a nylon cloth. These two substrates thus prepared were attached to
each other through a 5 .mu.m spacer so that the rubbing directions were at
a right angle to each other.
On the surface of the cell thus prepared, a photo-mask 3 was disposed as
shown in FIG. 5. Moreover, a uniform mixture of 0.55 g of stearyl
acrylate, 0.15 g of 1,4-butanediol acrylate, 0.20 g of styrene, 0.10 g of
the polymeric compound X used in Example 11, 13.3 g of a liquid crystal
material, ZLI-4792 (manufactured by Merck, Inc.; .DELTA.n=0.094; the twist
angle was adjusted to 90.degree. by using a chiral material;, S811), and
0.04 g of a photoinitiator (Irgacure 651) was injected into the cell by a
capillary tube. Then, a TN mode liquid crystal display element having
liquid crystal regions surrounded by a polymer wall was prepared by the
same procedure as in Examples 9-13.
Polarizing plates were attached to both surfaces of the element thus
prepared so that the polarization axes of the polarizing plates
corresponded to the respective rubbing direction.
The liquid crystal of the element thus prepared was in the TN orientation
with a uniform orientation state. Moreover, the display characteristics of
the element were not varied, even when the outer surface of the element
was pressed by a pen.
Example 19
A polyimide film (Sunever; manufactured by Nissan Chemical, Inc.) was
applied to 1.1 mm glass substrates having ITO (a mixture of indium oxide
and tin oxide; having a thickness of 500 angstrom) transparent electrodes
formed by the spin coating method, and subjected to the rubbing treatment
with a nylon cloth. These two substrates thus prepared were attached to
each other through a 9.mu.m spacer so that the rubbing directions were at
an angle of 240.degree. to each other.
On the surface of the cell thus prepared, a photo-mask 3 was disposed as
shown in FIG. 5. Moreover, a uniform mixture of 0.55 g of stearyl
acrylate, 0.15 g of 1,4-butanediol acrylate, 0.20 g of styrene, 0.10 g of
the polymeric compound X used in Example 11, 13.3 g of a liquid crystal
material, ZLI-4427 (manufactured by Merck, Inc.; the twist angle was
adjusted to 240.degree. by using a chiral material, S811), and 0.04 g of a
photoinitiator (Irgacure 651) was injected into the cell by a capillary
tube. Then, a STN mode liquid crystal display element having liquid
crystal regions surrounded by a polymer wall was prepared by the same
procedure as in Examples 9-13.
Polarizing plates were attached to both surfaces of the element thus
prepared so that each of the polarization axes of the polarizing plates
was at an angle of 45.degree. from the rubbing direction and they were at
an angle of 105.degree. to each other.
The liquid crystal of the element thus prepared was in the STN orientation
with a uniform orientation state. Moreover, the display characteristics of
the element were not varied, even when the outer surface of the element
was pressed by a pen.
Example 20
A polyimide film (Sunever; manufactured by Nissan Chemical, Inc.) was
applied to 1.1 mm glass substrates having ITO (a mixture of indium oxide
and tin oxide; having a thickness of 500 angstrom) transparent electrodes
formed by the spin coating method, and subjected to the rubbing treatment
with a nylon cloth. These two substrates thus prepared were attached to
each other through a 2 .mu.m spacer so that the rubbing directions were at
a right angle to each other.
On the surface of the cell thus prepared, a photo-mask 3 was disposed as
shown in FIG. 5. Moreover, a uniform mixture of 0.02 g of
polyethyleneglycol diacrylate (NK-ester A-200; manufactured by
Shin-Nakamura Chemical Industries, Inc.), 0.09 g of lauryl acrylate, 0.01
g of styrene, 0.08 g of the polymeric compound X used in Example 11, 0.80
g of a liquid crystal material, ZLI-4003 (manufactured by Merck, Inc.),
and 0.005 g of a photoinitiator (Irgacure 651) was injected into the cell
by a capillary tube. Then, a FLC mode (SSF type orientation) liquid
crystal display element having liquid crystal regions surrounded by a
polymer wall was prepared by the same procedure as in Examples 9-13.
Polarizing plates were attached to both surfaces of the element thus
prepared so that the polarization axes of the polarizing plates were at an
angle of 90.degree. to each other.
The liquid crystal of the element thus prepared was in the SSF orientation
with a uniform orientation state. Moreover, the display characteristics of
the element were not varied, even when the outer surface of the element
was pressed by a pen. Moreover, no disturbance of the orientation which
was generated in ordinary FLC mode elements occured when the surface of
the element was pressed.
Various other modifications will be apparent to and can be readily made by
those skilled in the art without departing from the scope and spirit of
this invention. Accordingly, it is not intended that the scope of the
claims appended hereto be limited to the description as set forth herein,
but rather that the claims be broadly construed.
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